JPH07291908A - Production of primary aminoamine-based compound - Google Patents

Abstract

PURPOSE:To provide a method capable of economically producing the objective primary aminoamine-based compound under an industrially advantageous conditions while suppressing formation of by-products such as a secondary amine or a tertiary amine. CONSTITUTION:An N-cyanoethylamide-based compound of the formula I (R<1> is H, a 1-21C alkyl or a 3-18C cyclic alkyl) or the formula II (R<2> is a single bond, a 1-21C alkylene or a 3-14 cyclic alkylene) is catalytically hydrogenated in the presence or absence of a solvent by using one or more hydrogenating catalysts selected from a Raney cobalt-based catalyst and a Raney nickel-based catalyst at 50-150 deg.C, preferably 80-120 deg.C to provide a primary amidoamine-based compound of the formula III or the formula IV. In order to maintaining catalytic activity and improve the yield of the objective compound, the reaction is preferably carried out in the presence of the solvent and an aliphatic ether compound of the formula V (R<3> and R<4> are each a 1-6C alkyl; (n) is 1 to 5) is preferably used as the solvent. Existence of 0.005 to equivalent weight based on the raw material compound of water can improve the reaction rate and shows excellent effects especially in a solventless system.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a primary amidoamine compound, and more particularly to a method for producing a corresponding primary amidoamine compound by catalytic hydrogenation of an N-cyanoethylamide compound. . The primary amidoamine-based compound, which is a reaction target, is used as a synthetic raw material and a modifier for polyamide resins, epoxy resins, polyurethane resins, and other resins, and also for surfactants, fiber treating agents, paper treating agents, printing inks, It is a useful material as a raw material for paints and cosmetics.

[0002]

2. Description of the Related Art A method for obtaining a corresponding primary amine compound by catalytic hydrogenation of a cyano compound is known. Usually, ammonia water or liquid ammonia is allowed to coexist in a reaction system to prevent deammonification and It suppresses by-products of primary amines and tertiary amines.

However, in this method, the manufacturing cost is high and the post-treatment of waste ammonia gas is complicated. Further, since ammonia is used, there are restrictions on the apparatus, and the regulations are strict. Further, depending on the use of the product, the quality may be adversely affected.

Generally, in a method for producing a corresponding amine by catalytic hydrogenation of a cyano compound in the presence of a solvent,
The degree of side reaction such as deamine reaction is greatly influenced by the kind of the solvent. So far, as a good solvent, ammonia water (Journal of the Organic Synthesis Society, 32 , 33 (1974)),
Liquid-methanol (J. Am. Chem. Soc., 68, 1867 (1940)),
Methanol, ethylene glycol (JP-A-50-160214
No.) etc. have been proposed.

However, according to the studies by the present inventors, when these solvents are applied to N-cyanoethylamide compounds, secondary amines and tertiary amines are remarkably produced as by-products, and the amide bond of the starting material is used in these solvents. As a result of the reaction with, the yield of the desired product is significantly reduced.

[0006]

DISCLOSURE OF THE INVENTION The present invention suppresses by-products of secondary amines and tertiary amines, and aims at a high yield.
It is an object of the present invention to provide a novel and useful method capable of economically producing a secondary amidoamine compound under industrially advantageous conditions.

[0007]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have obtained a predetermined effect by selecting a specific hydrogenation catalyst and a specific reaction temperature range. Moreover, I found that the post-processing was simplified,
The present invention has been completed based on these findings. I found the following facts.

That is, the method for producing a primary amidoamine-based compound according to the present invention is a general method in which the N-cyanoethylamide-based compound represented by the general formula (1) or (2) is catalytically hydrogenated to obtain a corresponding general compound. In producing the primary amidoamine compound represented by the formula (3) or the general formula (4), a Raney cobalt catalyst is used in the presence or absence of a solvent,
It is characterized by catalytic hydrogenation at 50 to 150 ° C.

R ¹ CONHCH ₂ CH ₂ CN (1) [In the formula, R ¹ represents a hydrogen atom, an alkyl group having ^{1 to} 21 carbon atoms or a cyclic alkyl group having 3 to 13 carbon atoms. ]

R ² (CONHCH ₂ CH ₂ CN) ₂ (2) [In the formula, R ² represents a single bond, an alkylene group having 1 to 21 carbon atoms or a cyclic alkylene group having 3 to 14 carbon atoms. ]

R ¹ CONHCH ₂ CH ₂ CH ₂ NH ₂ (3) [In the formula, R ¹ has the same meaning as in formula 1. ]

R ² (CONHCH ₂ CH ₂ CH ₂ NH ₂ ) ₂ (4) [In the formula, R ² has the same meaning as in formula 2. ]

The primary amidoamine compound represented by the general formula (3) is produced by catalytically hydrogenating the monocyanoamide compound represented by the general formula (1) according to the method of the present invention. .

The monocyanoamide compound is N
-Cyanoformamide, N-cyanoethylacetamide, N-cyanoethylpropionic acid amide, N-cyanoethylbutyric acid amide, N-cyanoethyllauric acid amide, N-cyanoethylmyristate amide, N-cyanoethylpalmitic acid amide, N-cyanoethylstearic acid amide, Examples include N-cyanoethylcyclohexanecarboxylic acid amide.

The primary amidoamine compound represented by the general formula (4) is produced by catalytically hydrogenating the dicyanodiamide compound represented by the general formula (2) according to the method of the present invention.

As the dicyanodiamide compound,
N, N'-dicyanoethyl oxalic acid diamide, N, N '
-Dicyanoethyl malonic acid diamide, N, N'-dicyanoethyl succinic acid diamide, N, N'-dicyanoethyl glutaric acid diamide, N, N'-dicyanoethyl adipic acid diamide, N, N'-dicyanoethyl azelaic acid diamide , N, N'-dicyanoethyl azelaic acid diamide, N, N'-dicyanoethyl sebacic acid diamide,
N, N'- dicyanoethyl cyclohexane dicarboxylic acid diamide etc. are illustrated.

Examples of the hydrogenation catalyst according to the present invention include Raney cobalt-based catalysts such as Raney cobalt and Raney cobalt-manganese, and Raney nickel-based catalysts such as Raney nickel and Raney nickel-manganese. Raney cobalt-based catalysts are particularly recommended. . These are alloys each of which is developed with aluminum in an ordinary manner.

In the case of Raney cobalt as the alloy composition,
Cobalt 20-60%, Aluminum 80-40%
A composition within the range is suitable. In the case of Raney cobalt / manganese, the former alloy is 1 to 50%, preferably 2 to 2%.
Alloys containing 0% manganese are preferred.

In the case of Raney nickel, nickel is 2
A composition in the range of 0 to 60% and aluminum in the range of 80 to 40% is suitable. In the case of Raney cobalt manganese,
An alloy containing 1 to 50%, preferably 2 to 20% of manganese in the former alloy is preferable.

The amount of the hydrogenation catalyst used is 0.1 to 30% by weight, preferably 1 to 20% by weight, based on the N-cyanoethylamide compound in terms of alloy. If it is 0.1% by weight or less, it is difficult to obtain a practical reaction rate, and if it is 30% by weight or more, it is economically disadvantageous.

The hydrogenation catalyst can be used repeatedly.

This reaction is possible without using a solvent, but in order to maintain the activity of the catalyst and further improve the yield of the desired primary amine compound, the reaction is carried out in the presence of a solvent. Preferably.

When the starting material N-cyanoethylamide compound has a high melting point, for example, in the general formula (1), R ¹ is a monocyanoamide compound or a general formula (2) in which R ¹ is an alkyl group having 7 to 21 carbon atoms. ), R ² has 4 to 4 carbon atoms.
When hydrogenating the dicyanodiamide compound which is the alkyl group of 21, it is preferable to use a solvent.

The solvent recommended in this reaction is
An aliphatic ether compound having a large polarity and having no active hydrogen represented by the general formula (5) can be mentioned. Compared with methanol and ethylene glycol which have been conventionally used as a reaction solvent, this compound does not inactivate a hydrogenation catalyst and has less secondary and tertiary amine by-products.

R ³ O (CH ₂ CH ₂ O) n-R ⁴ (5) [In the formula, R ³ and R ⁴ are the same or different and each represents an alkyl group having 1 to 6 carbon atoms. n represents an integer of 1 to 5. ]

Examples of the aliphatic ether compound include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether ethylene glycol dibutyl ether, triethylene glycol. Examples thereof include dimethyl ether, and ethylene glycol dimethyl ether and ethylene glycol diethyl ether are particularly recommended.

A suitable amount of the solvent used is about 0.01 to 10 times by weight, preferably about 0.1 to about 1 times by weight that of the N-cyanoethylamide compound. If it is less than 0.01 times by weight, it is disadvantageous in terms of maintaining the activity of the catalyst and solubility of the high-melting-point raw material, and even if it is used in excess of 10 times by weight, no particularly excellent effect is recognized and it is economically disadvantageous. Is.

Further, by carrying out the hydrogenation reaction according to the present invention in the presence of a predetermined amount of water, it is possible to improve the hydrogenation reaction rate without impairing the high selectivity. This effect is remarkable in the solventless system.

The appropriate amount of water is 0.005 to 1 times by weight with respect to the N-cyanoethylamide compound as a reaction raw material, with or without the use of a reaction solvent. About 0.01 to 0.5 times by weight is recommended. If the amount is less than 0.005 times by weight, the effect is small, and if the amount exceeds the equivalent weight, the yield of the reaction target product tends to decrease.

The reaction temperature of the hydrogenation reaction is 50 to 150.
C., preferably 80 to 120.degree. If the temperature is lower than 50 ° C, a practical reaction rate cannot be obtained. On the other hand, if the temperature is higher than 150 ° C, deammonia and amide bond cleavage are remarkable, which is not preferable.

The reaction pressure is not particularly limited as long as a predetermined effect can be obtained, but usually 5 to 200 kg / cm.
² G, preferably 20 to 100 kg / cm ² G. 5 kg /
If it is less than cm ² G, it is difficult to obtain a practical reaction rate,
When it exceeds 0 kg / cm ² G, it is not preferable because it is restricted by the apparatus.

The reaction time varies depending on other reaction conditions, but is usually about 0.5 to 8 hours.

[0033]

EXAMPLES The present invention is described in detail below with reference to examples. The method of analyzing the product obtained in each example is as follows.
It is as follows.

(1) Total amine value According to AOCS Tf 1b-64, it is determined by titration with a N / 10 hydrochloric acid / isopropanol solution using a bromcresol green indicator.

(2) Amine Value Due to Secondary Amine and Tertiary Amine (Secondary and Tertiary Amine Value) According to AOCS Tf 2b-64, a primary amine was converted to a neutral compound with a 50% saltylaldehyde / isopropanol solution. After conversion, it is determined by the same titration as the above method.

(3) Primary amine value Calculated as a difference obtained by subtracting the secondary amine value from the total amine value.

(4) Theoretical Amine Value It is calculated from the molecular weight (Mw) of the N-cyanoethylamide compound according to the following formula. In the case of monocyanoamide Theoretical amine value = 56.1 x 1000
/ Mw In case of dicyanodiamide Theoretical amine value = 56.1 × 1000
× 2 / Mw

Example 1 In a 500 ml autoclave equipped with a magnetic stirrer, 150 g of N-cyanoethylpropionic amide, 50 g of diethylene glycol dimethyl ether and 5 g of expanded Raney cobalt / manganese catalyst (pre-expanded alloy composition Co: Mn: A
1 = 30.2: 3.9: 65.9) was charged, pressurized with hydrogen gas, and the hydrogenation reaction was performed at 110 ° C. while maintaining the pressure at 50 kg / cm ² G. Hydrogen absorption stopped completely in 125 minutes. Furthermore, the reaction was completed by keeping the same conditions for 30 minutes. This reaction product was filtered, and the reaction crude product obtained by removing the solvent under reduced pressure was analyzed.
Total amine value is 98.5%, secondary amine value is 2.0
%, The primary amine value was 96.5%.

Further, when the recovered catalyst was repeatedly used 10 times under the same conditions as above, the hydrogen absorption stop time was almost constant. When the reaction crude product after 10 times of repeated use of the catalyst was analyzed, the total amine value was 97.5%, the secondary amine value was 3.0%, and the primary amine value was relative to the theoretical amine value. Was 94.5%, which was almost the same quality as the first time.

Example 2 The hydrogenation reaction was carried out in the same manner as in Example 1 except that the solvent was not used. The first hydrogen absorption stopped completely in 135 minutes. The reaction crude product obtained in the same manner as in Example 1 was analyzed below to find that the total amine value was 9 with respect to the theoretical amine value.
The secondary amine value was 4.2%, the secondary amine value was 6.4%, and the primary amine value was 87.8%.

Example 3 A hydrogenation reaction was carried out in the same manner as in Example 1 except that 10 g of water was added. At this time, the hydrogen absorption time was 80 minutes. The reaction crude product obtained in the same manner as in Example 1 was analyzed below to find that the total amine value was 96.5 relative to the theoretical amine value.
%, Secondary amine value is 3.2%, primary amine value is 9
It was 3.3%.

Example 4 A hydrogenation reaction was carried out in the same manner as in Example 2 except that 5 g of water was added. At this time, the hydrogen absorption time was 100 minutes. The reaction crude product obtained in the same manner as in Example 1 was analyzed below to find that the total amine value was 95.1 with respect to the theoretical amine value.
%, Secondary amine value is 4.2%, primary amine value is 9%
It was 0.9%.

Example 5 N-cyanoethylstearic acid amide was used as a raw material, and a Raney cobalt catalyst was used as a catalyst (alloy composition C before development).
The hydrogenation reaction was carried out in the same manner as in Example 1 except that o: Al = 49.4: 50.6) was used. Hydrogen absorption completely stopped in 105 minutes. The reaction crude product obtained in the same manner as in Example 1 was analyzed below to find that the total amine value was 98.2%, the secondary amine value was 2.0%, and the theoretical amine value was 2.0%.
The primary amine value was 96.2%.

Example 6 An autoclave similar to that of Example 1 was charged with 150 g of N, N'-dicyanoethylsebacic acid diamide, 100 g of diethylene glycol diethyl ether and 10 g of Raney cobalt-manganese catalyst, and the temperature was 120 ° C. and 100 kg / cm ^2.
The hydrogenation reaction was carried out at G. Hydrogen absorption completely stopped in 205 minutes. The reaction crude product obtained in the same manner as in Example 1 was analyzed below to find that the total amine value was 96.5%, the secondary amine value was 4.1%, and the primary amine was based on the theoretical amine value. The price was 92.4%.

Example 7 The same autoclave as in Example 1 was charged with 200 g of N-cyanoethylstearic acid amide, 100 g of diethylene glycol dibutyl ether and 6 g of Raney cobalt-manganese catalyst, and hydrogenated at 90 ° C. and 50 kg / cm ² G. went. Hydrogen absorption completely stopped in 225 minutes. The reaction crude product obtained in the same manner as in Example 1 was analyzed below to find that the total amine value was 96.0 relative to the theoretical amine value.
%, Secondary amine value is 2.0%, primary amine value is 9
It was 4.0%.

Further, as in Example 1, the catalyst was repeated 1 times.
I went 0 times. As a result, the hydrogen absorption time was 25 at the 10th time.
It was 0 minutes, the reaction time was almost constant, and no significant deactivation of the catalyst was observed. When the obtained crude product was analyzed,
The total amine value is 96.1% against the theoretical amine value, 2.3
The primary amine value was 3.5% and the primary amine value was 92.6%.

Example 8 A hydrogenation reaction was carried out in the same manner as in Example 1 except that Raney nickel was used as the catalyst. The first hydrogen absorption is 100
Completely stopped in minutes. The reaction crude product obtained in the same manner as in Example 1 was analyzed below.
Total amine value is 92.2%, secondary amine value is 10.3
%, The primary amine value was 81.9%.

Comparative Example 1 The hydrogenation reaction was carried out in the same manner as in Example 1 except that methanol was used as the solvent. The first hydrogen absorption stopped completely in 140 minutes. The reaction crude product obtained in the same manner as in Example 1 was analyzed below to find that the total amine value was 90.1%, the secondary amine value was 9.5%, and the theoretical amine value was 1%.
The primary amine value was 80.6%.

Further, as in Example 1, the catalyst was repeatedly used 10 times. As a result, at the 10th time, the hydrogen absorption time became as long as 280 minutes (it is considered that the catalyst was deactivated), and when the obtained crude product was analyzed, the total amine value was 80 with respect to the theoretical amine value. As low as 1%, 2
-The tertiary amine value was remarkably high at 21.1%. As a result, the primary amine value was 59.0%, and the deterioration in quality was remarkable.

Comparative Example 2 The hydrogenation reaction was carried out in the same manner as in Example 1 except that ethylene glycol was used as the solvent. The first hydrogen absorption is 1
It stopped completely in 30 minutes. The reaction crude product obtained in the same manner as in Example 1 was analyzed below to find that the total amine value was 89.2% of the theoretical amine value and the secondary and tertiary amine values were 1.
The primary amine value was 0.4% and the primary amine value was 78.8%.

Further, as in Example 1, the catalyst was repeatedly used 10 times. As a result, at the 10th time, the hydrogen absorption time became 390 minutes (it is considered that the catalyst was deactivated), and when the obtained crude product was analyzed, the total amine value was 65.5 relative to the theoretical amine value. %, The secondary amine value was 33.0%, and the primary amine value was 32.5%.

Comparative Example 3 The hydrogenation reaction was carried out in the same manner as in Example 1 except that the reaction temperature was 160 ° C. The first hydrogen absorption stopped completely in 45 minutes. The reaction crude product obtained in the same manner as in Example 1 was analyzed below to find that the total amine value was 71.3%, the secondary and tertiary amine value was 27.0%, and the primary amine was based on the theoretical amine value. The price was 44.3%.

[0053]

Industrial Applicability According to the method of the present invention, it is possible to industrially produce a primary amidoamine compound at low cost with high selectivity and high yield without using ammonia which is generally used industrially. it can.

Claims (3)

[Claims] 1. An N-cyanoethylamide compound represented by the general formula (1) or the general formula (2) is catalytically hydrogenated,
First represented by the corresponding general formula (3) or general formula (4)
When producing a primary amidoamine-based compound, one or more hydrogenation catalysts selected from the group consisting of Raney cobalt-based catalysts and Raney nickel-based catalysts are used in the presence or absence of a solvent at 50 to 150 ° C. A method for producing a primary amidoamine compound, which comprises catalytic hydrogenation. ^{_{R 1 CONHCH 2 CH 2 CN (}} 1) [ wherein, R ¹ represents a hydrogen atom, an alkyl group or a cyclic alkyl group having a carbon number of 3 to 13 1 to 21 carbon atoms. ^{_{] R 2 (CONHCH 2 CH 2}} CN) 2 (2) [ wherein, R ² is a single bond, an alkylene group or a cyclic alkylene group having a carbon number of 3 to 14 1 to 21 carbon atoms. ^{_{] R 1 CONHCH 2 CH 2 CH}} 2 NH 2 (3) [ wherein, R ¹ has the same meaning as the general formula 1. ^{_{] R 2 (CONHCH 2 CH 2}} CH 2 NH 2) 2 (4) [ wherein, R ² have the same meanings as in formula 2. ] 2. The method for producing a primary amidoamine compound according to claim 1, wherein the reaction solvent is an aliphatic ether compound represented by the general formula (5). ^{_{R 3 O (CH 2 CH 2}} O) n-R 4 (5) [ wherein, R ^3, R ⁴ are the same or different and each represents an alkyl group having 1 to 6 carbon atoms. n represents an integer of 1 to 5. ] 3. The first aspect according to claim 1 or 2, wherein the catalytic hydrogenation is carried out in the presence of 0.005-equal weight amount of water to the N-cyanoethylamide compound.
For producing a primary amidoamine compound.